环境污染及其防治 农用化学物质、有毒化学物质污染及其防治

X592200600820珠江干流河口水体有机氯农药的研究/杨清书(中科院广州地球化学研究所有机地球化学重点实验室)…∥中国环境科学/中国环境科学学会.-2005,25(增刊).-47~51环图X-58参考美国EPA标准对珠江干流河口表层水样颗粒相和溶解相有机氯农药进行定量分析,并对有机氯农药的含量及分布进行探讨,结果显示,洪季、枯季水体中有机氯农药总量(颗粒相和溶解相)分别是9.7~26.3ng/L、41.7~122.5ng/L;洪季、枯季HCHs总量分别为5.8~20.6ng/L、13.8~99.7ng/L,DDTs总量分别是0.52~1.13ng/L,其它有机氯农药总量分别为3.36~8.51ng/L、17.5~61.5ng/…     

城市污水处理厂水样中有机氯农药残留分析

建立了基于HLB固相萃取柱和气相色谱/电子捕获(GC/ECD)分析城市污水中有机氯农药的分析方法,对北京市五大城市污水处理厂———高碑店、北小河、酒仙桥、清河、方庄污水处理厂进出水水样中有机氯农药进行了分析。在5个污水处理厂的水样中共检出了6种有机氯类农药,分别是α-六六六、β-六六六、γ-六六六、δ-六六六、艾氏剂、4,4’-滴滴伊和异狄氏剂,浓度在0.2~76.4ng/L之间。方法对有机氯农药的回收率达到60.93%~141.50%,方法检测限为(0.27~2.90)ng/L。     

石油化工行业废水中有机氯农药残留分析

文章建立了基于HLB固相萃取柱和气相色谱/电子捕获(GC/ECD)分析水体中有机氯农药的方法,并对方法的回收率、灵敏度进行了评价,同时分析了北京市燕山石油化工有限公司五个典型企业排放废水中有机氯农药的浓度,发现存在六六六(HCHs),滴滴涕(DDT)等有机氯污染物,在5个采样点的水样中有机氯农药的浓度为(0.76～14.8)ng/L,其中六六六、滴滴涕的含量分别为(0.76～10.5)ng/L和(4.89～14.8)ng/L.方法对有机氯农药的空白加标回收率达到74.6%～118.4%,方法检测限为(0.27～2.90)ng/L.     

石油化工行业废水中有机氯农药残留分析

文章建立了基于HLB固相萃取柱和气相色谱，电子捕获（GC/ECD）分析水体中有机氯农药的方法．并对方法的回收率、灵敏度进行了评价，同时分析了北京市燕山石油化工有限公司五个典型企业排放废水中有机氯农药的浓度，发现存在六六六（HCHs）。滴滴涕（DDT）等有机氯污染物，在5个采样点的水样中有机氯农药的浓度为（0．76-14．S）ng／L。其中六六六、滴滴涕的含量分别为（0．76～10．5）ng/L和（4．89-14．8）ng/L。方法对有机氯农药的空白加标回收率达到74．6％-118．4％。方法检测限为（0．27～2．90）ng/L。     

丹江口水库库边降雨径流中有机氯农药赋存及风险评价

在南水北调中线源头区丹江口水库典型区域,根据不同土地利用类型修建了5组径流场来收集径流,研究了降雨径流水相及颗粒相中有机氯农药的分布特征及来源,并对其进行了风险评价.采用GC/MS对降雨径流中美国EPA优先控制的20种有机氯农药(OCPs)进行了检测分析.结果表明,径流颗粒物中有α-HCH和DDE两种有机氯农药检测出,而水相中仅有α-HCH一种有机氯农药检测出,不同利用类型土地径流颗粒物中OCPs含量的基本趋势为: 耕地(137.35ng/g)>果园(43.74ng/g) >山林(26.89ng/g),水相中OCPs含量的基本趋势为:耕地(1.94ng/L) >果园(1.90ng/L)>山林(1.19ng/L),说明耕地和果园受人为污染的影响,这和当地的开发情况也非常符合;同种土地利用类型径流中OCPs含量的基本趋势为: 10~15°耕地>5~10°耕地>0~5°耕地,由此可知,径流中OCPs含量随坡度的增加而增加,可能是由于坡度增大径流量也随之增大,降雨冲刷对土壤中有机氯农药的影响较大.对降雨径流中α-HCH和DDE进行源解析,α-HCH可能来自早期残留,部分也可能来自大气沉降;而DDE可能源之早期施用的DDT农药在好氧条件下分解产物.     

珠江干流河口水体有机氯农药的研究

参考美国EPA标准对珠江干流河口表层水样颗粒相和溶解相有机氯农药进行定量分析,并对有机氯农药的含量及分布进行探讨,结果显示,洪季、枯季水体中有机氯农药总量(颗粒相和溶解相)分别是9.7～26.3ng/L、41.7～122.5ng/L;洪季、枯季HCHs总量分别为5.8～20.6ng/L、13.8～99.7ng/L, DDTs总量分别是0.52～1.13ng/L、5.85～9.53ng/L,其它有机氯农药总量分别为3.36～8.51ng/L、17.5～61.5ng/L.珠江干流河口水体的DDT/(DDE+DDD)比值向口门方向有逐渐递增趋势,表明沿程(特别是东江网河区)不断有浓度相对较高的DDT输入或仍有新使用的DDT农药进入珠江干流水体.     

海水总汞的金膜电阻直接测定法

本文介绍了用 HZY1-1型金膜测汞仪直接测定海水总汞的方法。该方法检测下限为3ng/L,即用 20ml海水样品能够以95%置信度测出其中含有0.06ng的汞。文中讨论了仪器的测试条件、影响因素及其消除方法。设置参比平衡通路消除气流差异等因素引起仪器的漂移,提高测量精密度。分别测定含汞浓度为6～7ng/L及17ng/L 的海水样品,其相对标准偏差分别为10～15%及12%。     

固相萃取法测定水源水中的有机磷农药

采用固相萃取盘萃取水中的有机污染物,以大口径毛细管柱气相色谱法一火焰光度检测器（CGC/FPD）定量测定了水源水中的有机磷农药研究了10种有机磷农药的气相色谱法（GC－FPD）的分析条件结果表明均加标回收率的范围为50％～96％．方法的最低检测限为119～534ng/L．对某水厂水源水中的有机磷农药含量进行了分析测定,结果表明久效磷、敌百虫检出量较大,分别为 0.165μg/L和0.137μg/L,除草醚有痕量检出。     

汉江水体和鱼体内有机氯农药残留水平及积累特征分析

为了研究汉江流域水体中有机氯农药(OCPs)残留水平以及鱼体内有机氯农药积累特征,对汉江地表水和当地经常食用的黄颡鱼进行了采样分析。结果表明:汉江水体中HCHs含量为0.37~0.99ng/L,平均值为0.61ng/L,DDTs含量为0.64~1.52ng/L,平均值为1.12ng/L,远低于《地表水环境质量标准》(GB3838—2002)规定的限值;黄颡鱼肌肉中HCHs含量为0.18~0.89ng/g(湿重),平均值为0.48ng/g(湿重),DDTs含量为12.03~45.75ng/g(湿重),平均值为24.27ng/g(湿重),均符合《农产品安全质量无公害水产品安全要求》标准;黄颡鱼不同组织中OCPs含量表现为内脏鱼鳃肌肉,原因是内脏为有害物质消化吸收的主要场所,腮为水生动物直接从水中吸附有害物质的主要部位;黄颡鱼对有机氯农药的积累效应表现为DDTsHCHs,这与有机氯农药疏水性的分配系数Kow呈正相关;黄颡鱼肌肉中DDTs和HCHs造成的致癌风险简要评估表明,DDTs检出的最大浓度对人类可能存在潜在的致癌风险。     

武汉市地下水中酞酸酯污染物检测及来源分析

在武汉市区长江与汉江交界地带采集了具有代表性的地下水水样。采用固相萃取-气相色谱联用法对样品中的痕量邻苯二甲酸酯污染物进行定性定量分析,方法线性范围1ng/L～1000ng/L,检出限22ng/L～341ng/L。武汉市地下水中邻苯二甲酸酯的检出种类主要包括DBP、DEHP与DIBP等3大类。DBP污染最严重的地点在S1(东西湖区),浓度达1023.8ng/L;DEHP污染最严重的地点在S4(常青花园),浓度达481.0ng/L;DIBP污染最严重的地点在S9(唐家墩),浓度达237.8ng/L。将检测结果与武汉市湖泊水,长江、汉江武汉段,武汉市垃圾填埋场垃圾渗滤液中的PAEs污染物种类及浓度进行对照,并结合采样点周边环境与水文地质条件进行分析。确定了PAEs污染物的土壤淋滤作用,汉江、长江水体对地下水的补给以及垃圾填埋场垃圾渗滤液的渗滤作用是武汉市地下水PAEs污染物的主要来源。     

Effects of two sludge application on fractionation and phytotoxicity of zinc and copper in the soil

The potential harm of heavy metals is a primary concern in application of sludge to the agricultural land. A pot experiment was conducted to evaluate the effect of two sludges on fractionation of Zn and Cu in soil and their phytotoxicity to pakchoi. The loamy soil was mixed with 0%, 20%, 40%, 60% and 80% (by weight) of digested sewage sludge (SS) and composted sludge (SC). The additions of both sludges caused a significant raise in all fractions, resulting in that exchangeable (EXCH) and organic bound (OM) became predominance of Zn and organic bound Cu occupied the largest portion. There was more available amount of Zn and Cu in SS treatments than SC treatments. During the pot experiment, the concentration of Zn in EXCH, carbonate (CAR) and OM and Cu in EXCH and OM fractions decreased in all treatments, so their bioavailability reduced. Germination rate and plant biomass decreased when the addition rate was high and the best yield appeared in 20% mixtures at the harvest of pakchoi. The two sludges increased tissue contents of Zn and Cu especially in the SS treatments. Zn in pakchoi was not only in relationship to ΔEXCH and ΔCAR forms but also in ΔOM forms in the sludge-soil mixtures. Tissue content of Cu in pakchoi grown on SC-soils could not be predicted by ΔEXCH. These correlation rates between Zn and Cu accumulation in pakchoi and variation of different fractions increased with time, which might indicate that sludges represented stronger impacts on the plant in long-term land application.     

Intraspecific differences in effects of co-contamination of cadmium and

A hydroponic experiment was carried out to study intraspecific differences in the effects of different concentrations of cadmium (Cd)(0-10 mg/L) and arsenate (As(V)) (0-8 mg/L) on the growth parameters and accumulation of Cd and As in six wheat varieties Jing-9428, Duokang-1, Jingdong-11, Jing-411, Jingdong-8 and Zhongmai-8. The endpoints of wheat seedlings, including seed germination,biomass, root length and shoot height, decreased with increasing the Cd and As concentrations. Significant differences in seed germination, biomass, root length, shoot height and the accumulation of Cd and As were observed between the treatments and among the varieties (p ＜ 0.05). The lethal dosage 50% were about 20, 80, 60, 60, 80 and 20 mg As/L for Jing-9428, Duokang-1, Jingdong-11,Jing-411, Jingdong-8 and Zhongmai-8, respectively, and the corresponding values for Cd were about 30, 80, 20, 40, 60 and 10 mg Cd/L, respectively. Among the six varieties, Duokang-1 was found to be the most resistant to Cd and As toxicity, and Zhongmai-8 was the most sensitive to Cd and As co-contamination. The resistance of the six varieties was found dependant on the seedling uptake of Cd and As. Duokang-1 was the most suitable for cultivation in Cd and As co-contaminated soils.     

Toxic effects of acetochlor, methamidophos and their combination on nifH gene in soil

Toxic effects of two agrochemicals on nifH gene in agricultural black soil were investigated using denaturing gradient gel electrophoresis （DGGE） and sequencing approaches in a microcosm experiment. Changes of soil nifH gene diversity and composition were examined following the application of acetochlor, methamidophos and their combination. Acetochlor reduced the nifH gene diversity （both in gene richness and diversity index values） and caused changes in the nifH gene composition. The effects of acetochlor on nifH gene were strengthened as the concentration of acetochlor increased. Cluster analysis of DGGE banding patterns showed that nifH gene composition which had been affected by low concentration of acetochlor （50 mg/kg） recovered firstly. Methamidophos reduced nifH gene richness that except at 4 weeks. The medium concentration of methamidophos （150 mg/kg） caused the most apparent changes in nifH gene diversity at the first week while the high concentration of methamidophos （250 mg/kg） produced prominent effects on nifH gene diversity in the following weeks. Cluster analysis showed that minimal changes of nifH gene composition were found at 1 week and maximal changes at 4 weeks. Toxic effects of acetochlor and methamidophos combination on nifH gene were also apparent. Different nifH genes （bands） responded differently to the impact of agrochemicals： four individual bands were eliminated by the application of the agrochemicals, five bands became predominant by the stimulation of the agrochemicals, and four bands showed strong resistance to the influence of the agrochemicals. Fifteen prominent bands were partially sequenced, yielding 15 different nifH sequences, which were used for phylogenetic reconstructions. All sequences were affiliated with the alpha- and beta-proteobacteria, showing higher similarity to eight different diazotrophic genera.     

Arsenic uptake by arbuscular mycorrhizal maize （Zea mays L.） grown in an arsenic-contaminated soil with added phosphorus

The effects of arbuscular mycorrhizal (AM) fungus (Glomus mosseae) and phosphorus (P) addition (100 mg/kg soil) on arsenic (As) uptake by maize plants (Zea mays L.) from an As-contaminated soil were examined in a glasshouse experiment.Non-mycorrhizal and zero-P addition controls were included.Plant biomass and concentrations and uptake of As,P,and other nutrients,AM colonization,root lengths,and hyphal length densities were determined.The results indicated that addition of P significantly inhibited root colonization and development of extraradical mycelium.Root length and dry weight both increased markedly with mycorrhizal colonization under the zero-P treatments,but shoot and root biomass of AM plants was depressed by P application.AM fungal inoculation decreased shoot As concentrations when no P was added,and shoot and root As concentrations of AM plants increased 2.6 and 1.4 times with P addition,respectively.Shoot and root uptake of P,Mn,Cu,and Zn increased,but shoot Fe uptake decreased by 44.6%,with inoculation, when P was added.P addition reduced shoot P,Fe,Mn,Cu,and Zn uptake of AM plants,but increased root Fe and Mn uptake of the nonmycorrhizal ones.AM colonization therefore appeared to enhance plant tolerance to As in low P soil,and have some potential for the phytostabilization of As-contaminated soil,however,P application may introduce additional environmental risk by increasing soil As mobility.     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.     

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.     

Potential of plant polyphenol oxidases in the decolorization and removal of textile and non-textile dyes

In this study an effort has been made to use plant polyphenol oxidases; potato （Solanum tuberosum） and brinjal （Solanum melongena）, for the treatment of various important dyes used in textile and other industries. The ammonium sulphate fractionated enzyme preparations were used to treat a number of dyes under various experimental conditions. Majority of the treated dyes were maximally decolorized at pH 3.0. Some of the dyes were quickly decolorized whereas others were marginally decolorized. The initial first hour was sufficient for the maximum decolorization of dyes. The rate of decolorization was quite slow on long treatment of dyes. Enhancement in the dye decolorization was noticed on increasing the concentration of enzymes. The complex mixtures of dyes were treated with both preparations of polyphenol oxidases in the buffers of varying pH values. Potato polyphenol oxidase was significantly more effective in decolorizing the dyes to higher extent as compared to the enzyme obtained from brinjal polyphenol oxidase. Decolorization of dyes and their mixtures, followed by the formation of an insoluble precipitate, which could be easily removed simply by centrifugation.     

Effect of sorbed and desorbed Zn(Ⅱ) on the growth of a green alga (Chlorella pyrenoidosa)

Toxic effect of Zn(Ⅱ) on a green alga (Chlorella pyrenoidasa) in the presence of sepiolite and kaolinite was investigated.The Zn-free clays were found to have a negative impact on the growth of C.pyrenoidosa in comparison with control samples (without adding any clay or Zn(Ⅱ)).When Zn(Ⅱ) was added,the algae in the presence of clays could be better survived than the control samples,which was actually caused by a decrease in Zn(Ⅱ) concentration in the solution owing to the adsorption of Zn(Ⅱ) on the clays.When the solution system was diluted,the growth of algae could be further inhibited as compared to that in a system which had the same initial Zn(Ⅱ) concentration as in the diluted system.This in fact resulted from desorption of Zn(Ⅱ) from the zinc-contaminated clays,although the effect varied according to the different desorption capabilities of sepiolite and kaolinite.Therefore the adsorption and desorption processes of Zn(Ⅱ) played an important part in its toxicity,and adsorption and desorption of pollutants on soils/sediments should be well considered in natural eco-environmental systems before their risk of toxicity to aquatic organisms was assessed objectively.